Geochemistry and K-Ar dates of the Mazagan granodiorite at V30-225, VA79-96KD and DSDP Hole 79-544A, off Moroccan coast

Gneissic granodiorite was recovered by drilling at the base of the Mazagan escarpment, 100 km west of the Casablanca, Morocco, at 4000 m water depth. Coarse, predeformative muscovite yielded dates of -515 Ma, fine-grained muscovite of -455 Ma, biotite -360 and 335 Ma, and feldspar -315 Ma. These dates are tentatively correlated with the microscopic results. We assume a minimum age of middle Cambrian for the granodiorite, an Ordovician deformation and mylonitization, and a Late Carboniferous overprint under upper greenschist facies conditions.

Reflection microscopy and geochemistry at DSDP Leg 55 Holes

Magnetic properties of volcanic rocks are controlled mainly by the physical and chemical state of their constituent ferromagnetic minerals. The most important parameters determining magnetic properties are concentration, composition, grain size, and oxidation state. In sea floor basalts, the main ferromagnetic minerals are titanomagnetites which are either unoxidized or, more commonly, have undergone various degrees of posteruptive low-temperature oxidation to become cationdeficient titanomagnetites, or titanomaghemites. The effects of this low-temperature alteration are seen in the increase of Curie temperature and decrease of saturation magnetization and lattice parameter of ferromagnetic minerals (Readman and O'Reilly, 1972). It is now believed that titanomaghemitization of newly formed mid-ocean ridge crust proceeds with a time constant of about 1 m.y., accompanying drastic decrease of the intensity of the natural remanent magnetization (NRM) (Johnson and Atwater, 1977).

Minerals, geochemistry and x-ray power characteristics at DSDP Sites 54-424, 60-458 and 60-459

Secondary minerals filling veins and vesicles in volcanic basement at Deep Sea Drilling Project Sites 458 and 459 indicate that there were two stages of alteration at each site: an early oxidative, probably hydrothermal, stage and a later, low-temperature, less oxidative stage, probably contemporaneous with faulting in the tectonically active Mariana forearc region. The initial stage is most evident in Hole 459B, where low-Al, high Fe smectites and iron hydroxides formed in vesicles in pillow basalts and low-Al palygorskite formed in fractures. Iron hydroxides and celadonite formed in massive basalts next to quartz-oligoclase micrographic intergrowths. Palygorskite was found in only one sample near the top of basement in Hole 458, but it too is associated with iron hydroxides. Palygorskite has previously been reported only in marine sediments in DSDP and other occurrences. It evidently formed here as a precipitate from fluids in which Si, Mg, Fe, and even some Al were concentrated. Experimental data suggest that the solutions probably had high pH and somewhat elevated temperatures. The compositions of associated smectites resemble those in hydrothermal sediments and in basalts at the Galapagos mounds geothermal field. The second stage of alteration was large-scale replacement of basalt by dioctahedral, trioctahedral, or mixed-layer clays and phillipsite along zones of intense fracturing, especially near the bottom of Holes 458 and 459B. The basalts are commonly slickensided, and there are recemented microfault offsets in overlying sediments. Native copper occurs in one core of Hole 458, but associated smectites are dominantly dioctahedral, unlike Hole 459B, where they are mainly trioctahedral, indicating nonoxidative alteration. The alteration in both holes is more intense than at most DSDP ocean crust sites and may have been augmented by water derived from subducting ocean crust beneath the fore-arc region.

Geochemistry of basalts from ODP Hole 109-648B

Legs 106-109 achieved the first basaltic bare-rock drill hole, on a small volcano (Serocki volcano) located on the flanks of the rift valley in the MAR about 70 km south of the Kane fracture zone. Because of severe technical difficulties only 50.5 m of basalt below seafloor was recovered. Geochemical analysis shows that the recovered basalts display typical N-MORB characteristics as expected in this segment of the Mid-Atlantic ridge. The lava flows display rather equivalent geochemical characteristics all over the drilled section and show the imprint of a previous magmatic differentiation suffered by the magmas before their emission, indicative of a fractional crystallization of plagioclase-bearing cumulates. The incompatible and alkali element content of these 648B magmas is very low, a feature which resembles those of other N-MORB. The geochemical characteristics of these basalts look closely similar to those of basalts from the same flow line emitted respectively 10 m.y. (Hole 395, Legs 45-46), and 110 m.y. (Hole 417A, Legs 51-53) ago, supporting the persistence in this ridge segment of a mantle source with depleted characteristics over the last 110 m.y., but with some variations in the degree of depletion of the source along this period. Although these rocks appear fresh, the imprint of an incipient low temperature alteration can be noticed in a few samples, as evidenced by slight increases of alkali, U elements, and 87Sr/86Sr isotopic compositions.

Geochemistry of Neogene-Quaternary sediments in ODP Site 105-645

Subcontinuously cored early(?)-middle Miocene to recently deposited sediments from ODP Site 645 were studied texturally, mineralogically, and geochemically. The entire sequence contains minerals and associated chemical elements that are chiefly of detrital origin. In particular, the clay minerals, which include smectite, kaolinite, chlorite, and illite, are detrital. No obvious evidence of diagenesis with depth, of burial, of volcanism, or of hydrothermal alteration was observed. The sedimentary textures, clay mineralogy, and <2-µm fraction geochemistry of the early middle Miocene sediments (630 to 1147 mbsf) suggest the pronounced but variable influence of a southward bottom current. Two clay facies are defined. The lower one, Cj (780 to 1147 mbsf), is characterized by the great abundance of discrete smectite (with less than 15% illite interlayers), probably detrital in origin, and reworked older, discrete, smectite-rich sediments. The upper clay facies, C2 (630 to 780 mbsf), shows a net decrease of the fully expandable clay abundances, with a great abundance of mixed-layer, illite-smectite clays (60 to 80% of illite interlayers). Such clay assemblages can be inherited from paleosoils or older sedimentary rocks. An important change occurs at 630 mbsf (clay fraction) or 600 mbsf (sedimentary texture), which may be explained by the beginning of continental glaciation (630 mbsf, ~9 Ma) and the onset of ice rafting in Baffin Bay (600 mbsf, ~8 Ma). Above this level, the characteristics and modifications of the clay assemblages are controlled climatically and can be explained by the fluctuations of (1) ice-rafting, (2) speed of weak bottom currents, and (3) some supply by mud turbiditic currents. Three clay facies (C3, C4, and C5) can be defined by the abrupt increases of the inherited chlorite and illite clays.

Inorganic and organic geochemistry and sediment descriptions at DSDP Hole 93-603B

About one hundred samples of sediments and rocks recovered in Hole 603B were analyzed for type, abundance, and isotopic composition of organic matter, using a combination of Rock-Eval pyrolysis, C-H-N-S elemental analysis, and isotope-ratio mass spectrometry. Concentrations of major, minor, and trace inorganic elements were determined with a combination of X-ray fluorescence and induction-coupled plasma spectrometry. The oldest strata recovered in Hole 603B (lithologic Unit V) consist of interbedded light-colored limestones and marlstones, and black calcareous claystones of Neocomian age. The inorganic and organic geochemical results suggest a very terrigenous aspect to the black claystones. The organic geochemical results indicate that the limestones and marlstones contain a mixture of highly degraded marine and terrestrial organic matter. Comparison of the Neocomian carbonates at Site 603 with those on the other side of the North Atlantic, off Northwest Africa at Site 367, shows that the organic matter at Site 367 contains more marine organic matter, as indicated by higher pyrolysis hydrogen indices and lighter values of d13C. Comparison of inorganic geochemical results for the carbonate lithologies at Site 603 with those for carbonate lithologies at Site 367 suggests that the Site 603 carbonates may contain clastic material from both North American and African sources. The black claystones at Site 603, on the other hand, probably were derived almost entirely from North American clastic sources. Lithologic Unit IV overlying the Neocomian carbonates, consists of interbedded red, green, and black claystones. The black claystones at Site 603 contain more than ten times the organic carbon concentration of the interbedded green claystones. The average concentration of organic carbon in the black claystones (2.8%), however, is low relative to most mid-Cretaceous black claystones and shales in the Atlantic, particularly those found off Northwest Africa. The geochemical data all suggest that the organic matter in the black claystones is more abundant but generally more degraded than the organic matter in the green claystones, and that it was derived mainly from terrestrial sources and deposited in oxygenated bottom waters. The increased percentage of black claystone beds in the upper Cenomanian section, and the presence of more hydrogen-rich organic matter in this part of the section, probably resulted from the increased production and accumulation of marine organic matter that is represented worldwide near the Cenomanian/Turonian boundary in deep-sea and land sections. A few upper Cenomanian black claystone samples that have hydrogen indices > 150 also contain particularly high concentrations of V and Zn. Most samples of black claystone, however, are not particularly metal-rich compared with other black claystones and shales. Compared with red claystones from lithologic Unit IV, the green and black claystones are enriched in many trace transition elements, especially V, Zn, Cu, Co, and Pb. The main difference between the "carbonaceous" claystones of lithologic Unit IV and "variegated" or "multicolored" claystones of the overlying Upper Cretaceous to lower Tertiary Unit III is the absence of black claystone beds. As observed at several other sites (105 and 386), the multicolored claystones at Site 603 are somewhat enriched in several trace transition elements-especially Cu, Ni, and Cr-relative to most deep-sea clays. The multicolored claystones are not enriched in Fe and Mn, and therefore are not "metalliferous" sediments in the sense of those found at several locations in the eastern Pacific. The source of the slightly elevated concentrations of transition metals in the multicolored claystones probably is upward advection and diffusion of metals from the black claystones of the underlying Hatteras Formation. The red, orange, and green claystone beds of lithologic Unit II (Eocene), like those of Unit III, really represent a continuation of deposition of multicolored claystone that began after the deposition of the Neocomian carbonates. The color of the few black beds that occur within this unit results from high concentrations of manganese oxide rather than high concentrations of organic matter.

Geochemistry and fluxes at DSDP Hole 83-504B

This chapter documents the chemical changes produced by hydrothermal alteration of basalts drilled on Leg 83, in Hole 504B. It interprets these chemical changes in terms of mineralogical changes and alteration processes and discusses implications for geochemical cycling. Alteration of Leg 83 basalts is characterized by nonequilibrium and is heterogeneous on a scale of centimeters to tens or hundreds of meters. The basalts exhibit trends toward losses of SiO2, CaO, TiO2; decreases in density; gains of MnO, Na2O, CO2, H2O+ , S; slight gains of MgO; increased oxidation of Fe; and variable changes in A12O3. Some mobility of rare earth elements (REE) also occurred, especially the light REE and Eu. The basalts have lost Ca in excess of Mg + Na gains. Variations in chemical trends are due to differing water/rock ratios, substrate control of secondary mineralogy, and superimposition of greenschist and zeolite facies mineralogies. Zeolitization resulted in uptake of Ca and H2O and losses of Si, Al, and Na. These effects are different from the Na uptake observed in other altered basalts from the seafloor attributed to the zeolite facies and are probably due to higher temperatures of alteration of Leg 83 basalts. Basalts from the transition zone are enriched in Mn, S, and CO2 relative to the pillow and dike sections and contain a metal-sulfide-rich stockwork zone, suggesting that they once were located within or near a hydrothermal upflow zone. Samples from the bottom of the dike section are extensively fractured and recrystallized indicating that alteration was significantly affected by local variations in permeability.

Geochemistry and minerals of glass shards at DSDP Leg 66 Holes

Deep Sea Drilling Project Leg 66 drilled eight sites along a transect across the Middle America Trench off Mexico, including continental (Sites 493 and 489), oceanic (Site 487), and trench (Site 486) reference sites and four sites (490, 492, 491, 488) in the trench inner wall. Because of their location - close to volcanic sources and subject to prevailing winds and marine currents (N to S, NW to SE) - analysis of airborne ashes intercalated within the sediments at these sites provides a reliable record of explosive volcanism in the area. Intense onshore volcanic activity in Mexico during the Oligo-Miocene has been well documented by the andesites and ignimbrites of the Sierra Madre Occidental and Sierra Madre del Sur and in the Plio-Quaternary by the andesites and basalts from the Trans-Mexican Neovolcanic Belt and the eastern border of Baja California.

Geochemistry of eolian dust from sediment core LL44-GPC-3

The large-diameter piston core LL44-GPC3 from the central North Pacific Ocean records continuous sedimentation of eolian dust since the Late Cretaceous. Two intervals resolved by Nd and Pb isotopic data relate to dust coming from America (prior to ~40 Ma) and dust coming from Asia (since ~40 Ma). The Intertropical Convergence Zone (ITCZ) separates these depositional regimes today and may have been at a paleolatitude of ~23°N prior to 40 Ma. Such a northerly location of the ITCZ is consistent with sluggish atmospheric circulation and warm climate for the Northern Hemisphere of the early to middle Eocene. Since ~40 Ma, correlations between Nd (~7.55 > epsilon-Nd(t) > ~10.81) and Pb (18.625 < 206/4Pb < 18.879; 15.624 < 207/4Pb < 15.666; 38.611 < 208/4Pb < 38.960; 0.8294 < 207/6Pb < 0.8389; 2.0539 < 208/6Pb < 2.0743) isotopes reflect the progressive drying of central Asia triggered by the westward retreat of the paleo-Tethys. Comparisons between the changes with time in the isotopically well-defined dust flux and Nd and Pb isotopic compositions of Pacific deep water allow one to draw two major conclusions: (1) dust-bound Nd became a resolvable contribution to Pacific seawater only after the one order of magnitude increase in dust flux starting at ~3.5 Ma. Therefore eolian Nd was unimportant for Pacific seawater Nd prior to 3.5 Ma. (2) The lack of a response of Pacific deep water Pb to this huge flux increase suggests that dust-bound Pb has never been important. Instead, mobile Pb associated with island arc volcanic exhalatives probably consists of a significant contribution to Pacific deep water Pb and possibly to seawater elsewhere far away from landmasses.

Organic geochemistry of ODP Leg 107 sediments

The Rock-Eval pyrolysis of rock samples and the elemental analysis of kerogens show clear differences between Messinian black shales and Pliocene-Pleistocene sapropels recovered during ODP Leg 107. The Messinian black shales are characterized by a large variety of compositions which probably reflects a great diversity of depositional and diagenetic paleoenvironments. In contrast, the Pliocene-Pleistocene sapropels, occurring as discrete layers in nannofossil oozes barren of organic carbon, constitute a rather homogeneous group in terms of organic content. A considerable contribution of terrestrial organic matter in the sapropels could mean that an identical phenomenon of terrestrial input has been periodically reproduced in the basin. The maturity and the nature of the organic matter are discussed with respect to anomalous values recorded for Tmax parameter.

Geochemistry and foraminiferal stable isotoe record of sediment core SCS90-36

Changes in the Southeast Asia monsoon winds and surface circulation patterns since the last glaciation are inferred using multiple paleoceanographic indicators including planktic foraminifer faunal abundances, fauna and alkenones sea-surface temperature (SST) estimates, oxygen and carbon isotopes of planktic and benthic foraminifers, and sedimentary fluxes of carbonates and organic carbon obtained from deep-sea core SCS90-36 from the South China Sea (SCS) (17°59.70'N, 111°29.64'E at water depth 2050 m). All these paleoceanographic evidences indicate marked changes in the SCS ocean system over the last glacial toward the Holocene. Planktic foraminiferal faunal SST estimates show stable warm-season SST of 28.6°C, close to the modern value, throughout the glacial-interglacial cycle. In contrast, cold-season SST increases gradually from 23.6°C in the last glacial to a mean value of 26.4°C in the Holocene with a fluctuation of about 3°C during 13-16 ka. SST estimates by UK'37 method reveal less variability and are in average 1-3°C lower than the fauna-derived winter-season SST. These patterns reveal that the seasonality of the SST is not only higher by about 3-4°C in the glacial, but also a function of the winter season SST. Sedimentation rates decrease from the last glacial-deglacial stage to the Holocene due to a reduction in supply of terrigenous components, which led to an increase of carbonate contents. Total organic carbon (TOC) contents of primarily marine sources decrease from the last glacial-deglacial to the Holocene. The last deglaciation is also characterized by high surface productivity as indicated by increased ketones abundances and high mass accumulation rates (MAR) of the TOC and carbonates. The gradient of planktic foraminifer ocygen and carbon isotopes of between surface dwellers and deep dwellers increases significantly toward Termination I and Holocene, and is indiscernibly small in the carbon isotope gradient of between 14 and 24 ka, revealing a deep-mixing condition in surface layers prior to 10 ka. The glacial-interglacial fluctuation of the carbon isotope value of a benthic foraminifer is 0.61%. which is significantly larger than a global mean value. The large carbon isotope fluctuation indicates an amplification of marginal-sea effects which is most likely resulted from an increase in surface productivity in the northern SCS during the last glacial-deglacial stage. The multiple proxies consistently indicate that the last glacial-deglacial stage winter monsoon in the Southeast Asia was probably strengthened in the northern SCS, leading to a development of deep-mixing surface layer conditions and a more efficient nutrient cycling which supports more marine organic carbon production.

Geochemistry of ODP Site 123-765 sediments

Drilling at Site 765 in the Argo Abyssal Plain sampled sediments and oceanic crust adjacent to the Australian margin. Some day, this site will be consumed in the Java Trench. An intensive analytical program was conducted to establish this site as a geochemical reference section forcrustal recycling calculations. About 150 sediment samples from Site 765 were analyzed for major and trace elements. Downhole trends in the sediment analyses agree well with trends in sediment mineralogy, as well as in Al and K logs. The primary signal in the geochemical variability is dilution of a detrital component by both biogenic silica and calcium carbonate. Although significant variations in the nonbiogenic component occur through time, its overall character is similar to nearby Canning Basin shales, which are typical of average post-Archean Australian shales (PAAS). The bulk composition of the hole is calculated using core descriptions to weight the analyses appropriately. However, a remarkably accurate estimate of the bulk composition of the hole can be made simply from PAAS and the average calcium carbonate and aluminum contents of the hole. Most elements can be estimated within 30% in this way. This means that estimating the bulk composition of other sections dominated by detrital and biogenic components may require little analytical effort: calcium carbonate contents, average Al contents, and average shale values can be taken from core descriptions, geochemical logs, and the literature, respectively. Some of the geochemical systematics developed at Site 765 can be extrapolated along the entire Sunda Trench. However, results are general, and Site 765 should serve as a useful reference for estimating the compositions of other continental margin sections approaching trenches around the world (e.g., outboard of the Lesser Antilles, Aegean, and Eolian arcs).

Inorganic major, minor, and trace element geochemistry and clay mineralogy of sediments from the Deep Sea Drilling Project Leg 96, Gulf of Mexico

Sediment samples collected at DSDP Leg 96 Mississippi Fan Sites 615, 616, 620, 621, and 623, Orca Basin Site 618, and Pigmy Basin Site 619 were analyzed for 22 major, minor, and trace elements. This study was undertaken to document the downhole variability in inorganic geochemistry between sites. The mineralogy of the clays, including those from Sites 614, 617, and 622 on the fan, was determined by X-ray diffraction to define the principal clay minerals present at the sites, examine any downhole trends in clay mineralogy, and aid in the interpretation of the geochemical signature of the sediments. Clay mineral composition at all the sites is smectite:illite:chlorite:kaolinite in the approximate percentage ratio 50:20:20:10. Geochemical results indicate only slight variation between and within the sites, with the exception of a discrete unit of carbonates that occurs near the bottom of Site 615. Variation in the major, minor, and trace element composition can be explained by a change in the relative abundance of quartz, clay minerals, and carbonates.

Geochemistry of neritic carbonates of ODP Hole 134-831B

Drilling at Bougainville Guyot (Ocean Drilling Program Site 831), New Hebrides Island Arc during Leg 134 revealed that 727.5 m of carbonate overlies an andesite basement. The carbonate cap at Site 831 consists of 20 m of pelagic carbonate overlying 707.5 m of neritic carbonates. The neritic section consists of ~230 m of largely unaltered aragonite sediment that overlies ~497 m of totally calcitized limestone. The deeper portion of the calcitized interval has been pervasively altered by diagenesis. Prior to this study the age distribution of sediments at Bougainville Guyot was poorly known because age diagnostic fossils are sparsely and discontinuously distributed in the sequence. We have used Sr isotopes to provide temporal constraints on the deposition of carbonates at Site 831; these constraints are critical in reconstructing the vertical movement of Bougainville Guyot before its collision with the New Hebrides Island Arc. Overall, the chronostratigraphy of Bougainville Guyot can be subdivided into three intervals: (1) a Pleistocene interval (102.4 to 391.11 meters below sea floor [mbsf]); (2) a Miocene interval (410.31 to 669.53 mbsf); and (3) an Oligocene interval (678.83 to 727.50 mbsf). Strontium isotopic ages of samples increase with increasing depth in the carbonate sequence, except near the bottom of the sequence, where several samples exhibit a consistent reversed age vs. depth trend. Such age reversals are most likely the product of post-depositional rock-water interaction. Preliminary stable isotope data are consistent with diagenetic alteration in the marine and meteoric environments. Several abrupt decreases in d87Sr, and hence age, of sediments are recognized in the carbonate cap at Bougainville Guyot. These disconformities are most likely the product of subaerial exposure in response to relative sea-level fall. Indeed, Sr-isotope ages indicate that 2 to 9 m.y. of sediment deposition is missing across these d87Sr disconformities.

Age determination and Argon geochemistry of Hawaiian Emperor seamounts

The Hawaiian-Emperor bend has played a prominent yet controversial role in deciphering past Pacific plate motions and the tempo of plate motion change. New ages for volcanoes of the central and southern Emperor chain define large changes in volcanic migration rate with little associated change in the chain's trend, which suggests that the bend did not form by slowing of the Hawaiian hot spot. Initiation of the bend near Kimmei seamount about 50 million years ago (MA) was coincident with realignment of Pacific spreading centers and early magmatism in western Pacific arcs, consistent with formation of the bend by changed Pacific plate motion.